TW201026668A - Crystalline complexes of pendimethalin and metazachlor - Google Patents

Abstract

The present invention relates to crystalline complexes of pendimethalin and metazachlor. It also relates to agriculturally useful compositions of the complexes.

Description

201026668 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a crystalline complex of PENDIMETHALIN and METAZACHLOR. The invention also relates to compositions in which the complex is suitable for use in agriculture. [Prior Art] Agricultural active organic compounds (such as fungicides, herbicides, and insecticides or acaricides) are usually sold as liquid or solid formulations containing one or several agriculturally active organic compounds and suitable formulation additives. . For some reason, if the agriculturally active organic compound is present in a solid form, it is preferably a formulation type, and examples thereof include a solid preparation (such as dust powder, powder or capsule) and a liquid preparation (such as a suspension concentrate, that is, An aqueous composition comprising an active organic compound dispersed in an aqueous medium as a fine particle). Suspended concentrates have desirable liquid characteristics that can be poured or pumped and easily diluted with water to the desired concentration for application. In contrast to emulsion concentrates, another advantage of suspension concentrates is that they do not require the use of organic solvents that are not miscible with water. For this solid form formulation, the agricultural compound should be a crystalline material having a sufficiently high melting point. Unfortunately, most of these agriculturally active compounds are amorphous materials and/or have a low melting point, resulting in processing difficulties, unstable formulations, and reliability due to agglomeration or sinking of fine particles. These problems are apparent in the herbicide application ® (PEND surface THALIN, N-(l-= propyl propyl dinitroaniline common name), because of the low melting point of 55 to 57 C, And even if there are a small amount of impurities or a formulation additive, the melting point will further decrease. 143730.doc 201026668 Another problem is that the sputum tends to form large crystals during the ripening process, increasing the amount of particle precipitation and thus causing instability. Difficulty in processing and no reliable use. This problem is exacerbated by the storage of a hydrophobic suspension concentrate at temperatures above 35 ° C and particularly above 4 ° C. US 4,874,425 discloses an aqueous concentration combination of applied hydrazine. Containing sodium lignosulfonate or calcium lignosulfonate as a stabilizer. EP 249 770 discloses a stable suspension concentrate of sputum, which is prepared by emulsifying molten enthalpy in hot water, adding a surfactant and defoaming. The agent is provided to provide a droplet of the droplets having a droplet size of about 2 to 10 microns, and the hot emulsion is stirred to cool to ambient temperature. EP-A-823 993 teaches an aqueous microcapsule composition comprising the use of pH The application of a microencapsulated sensitizing polymeric material to microencapsulation. Another method for improving the applicability of low melting point organic formulations for use in aqueous formulations is to provide higher melting crystalline complexes of such organic formulations, and thus can produce fine Stable aqueous suspension of granules. Crystalline complexes of organic compounds, also known as cocrystals, are multicomponent crystals or different organic compounds or at least one non-volatile oil which are usually solid at 25t: 25t: lower vapor pressure is lower than 丨 mbar) composition = crystal material. In the crystal complex (or co-crystal), at least two different organic compounds form a crystal material having a crystal structure, that is, at least two The organic compound has a defined relative spatial arrangement in the crystal structure. In the co-crystal, the at least two different compounds are non-covalent bonds (such as hydrogen bonds and possibly other packages, heaps 4, dipole interaction forces, and van der Waals).瓦143730.doc 201026668 Force non-covalent intramolecular force) bonding. Although it is impossible to design or predict the filling of crystal lattice, it can successfully identify the joint Several supramolecular synthons in the body. The term "supramolecular synthesis" is understood to mean that two compounds are usually formed by a non-covalent bond structure. In the co-crystal, these composites are further filled with crystal grains. Molecular crystals form a molecular crystal. Molecular recognition is a prerequisite for the formation of a composite. However, co-crystals must also have the advantage of energy, that is, the energy required to form the co-crystals, because the molecules typically It is extremely effective to fill the crystal of pure components and hinder the formation of co-crystals. Among the co-crystals, one of the organic compounds can be used as a precursor of the co-crystal, that is, a crystal material can be easily formed by itself and can be different from others. A compound which forms a crystalline organic compound to form a cocrystal. Crystalline complexes of active pharmaceutical compounds have been described in the related art in various situations, for example, in US 2003/224006, WO 03/074474, WO 2005/089511, EP 1608339, EP 1631260, and WO2006/007448. Moxachlor (2-chloro-(2,6-dimethylphenyl)-indole-(1//-°bizozol-1-ylmethyl)acetamid) is well known for its three different polymerizations. a crystalline herbicide in the form of

One of the most thermodynamically stable forms is the monoclinic 143730.doc 201026668 crystal form known from EP 411 408. Its polymorphism is further described in 1^.1.〇1^8861*, 0· Weigand, JM Rollinger, M. Haddow, E. Gstrein (2004) in { J. Therm. Anal. Calorim·} Dijon 5's exhibition of rebellion. Weigand's doctoral thesis, Innsbruck, 2001. Its reported melting point is in the range of 76 ° C to 83 ° C. The herbicide is a group of chloroethenyl aniline and pyrazole herbicides. Shide is a crystal herbicide known by the following formula:

According to Stockton et al., mesalamine is present in triclinic and monoclinic crystal structures (see GW Stockton, R. Godfrey, P. Hitchcock, R. Mendelsohn, PC Mowery, S. Rajan, AF Walker, 1998) "J. C/zem. «Soc·, PerHw TVflw·?·" Vol. 2, p. 2061). The reported melting points are between 57 ° C and 55 ° C, respectively. The herbicide belongs to the dinitroaniline herbicide group. SUMMARY OF THE INVENTION The inventors have unexpectedly discovered that the application of hydrazine is a suitable co-crystal object capable of forming a crystalline complex with mesin. Accordingly, the present invention is directed to a crystalline complex comprising a ruthenium and a herbicide, and in particular a crystalline complex comprising a guanidine and a herbicide. [Embodiment] The crystalline complex according to the present invention has a defined crystal structure and has a reasonably high melting point, which facilitates the incorporation of the complex into a solid or liquid formulation containing the active 143730.doc 201026668 material in solid form. . Moreover, it is abundance and has a 'stable stability compared to a formulation comprising a mixture of sorghum and imazauride in a solid compound form and a dry makeup. Sex.

曰曰曰B It is hypothesized that the application of hydrazine and chlorfenaper has the ability to form an energy-favorable ligated compartment. Thus, a crystalline complex according to the present invention can be formed wherein the guanidine and the herbicide are arranged in a defined relative spatial order, The combination of the two molecules is such that the supramolecular composition of the crystal structure is represented.

In the crystalline complex according to the present invention, the ratio of the herbicide and the molybdenum is generally in the range of from 〇5:1 to 2:1, preferably in the range of from 8:1 to 125:1. Specifically, this molar ratio is between 0:9 and m, especially about 1:1. However, deviations may also occur, but typically do not exceed 2 mole percent, preferably no more than 10 mole percent. Crystalline complexes can be identified from simple mixtures of chloramine crystals and cerium crystals by standard analytical methods for the analysis of crystalline materials, including X-ray powder diffraction assays (PXRD) and thermochemical analysis. (such as thermal gravity analysis (TGA) and differential scanning calorimetry (DSC)). The relative content of the herbicide and the guanidine can be determined by HPLC or ih_nmr spectroscopy / the herbicide and the crystallized complex of the herbicide, and the pure compound is shown in the X-ray powder diffraction pattern of 25 (copper_radiation, A). The characteristic reflection peak has disappeared. In particular, the crystalline complex of imazachlor and acetonide exhibits at least *, preferably at least 6, particularly at least 8 and more preferably all of the lower = ^ in the form of a 2 Θ value and a lattice spacing d Represents the reflection peak. 143730.doc 201026668 Table 1: PXRD values of the herbicide and the crystallized complex of the herbicide (25 ° C, copper radiation, 1, 5406 A) 2 Θ value d 『 6.60 ± 0.2 13.89 ^ = 0.4 7.06 ± 0.2 12.54 = T〇.3 7.36±0.2 12.O0=t〇.3 11.82±0.2 7.48t〇.l 12.78±0.2 6.93±〇.08 14.72±0_2 6.01±0.05 19.21 Soil 0.2 4.62±O.03 21.28 Soil 0.2 4.17± O.03 22.15 Soil 0.2 4.01 ± 0.03 A single crystal study of the herbicide and the crystallized complex of samarium showed that the basic crystal structure is triclinic and has a space group P-1. Structural analysis revealed that the crystalline complex was a 1:1 mixture of mesin and guanidine, and the asymmetric unit contained one herbicide molecule and one ruthenium molecule. The spatial arrangement of the herbicide and the samarium molecule in the crystal appears to be driven primarily by an energetically favorable three-dimensional filling and the interaction between the dipole and the dipolar molecules and the weak hydrogen bonds. The characteristic data of the crystal structure is shown in Table 2. Table 2: Crystallographic data of the herbicide and the crystallographic complex of the applied hydrazine. Parameter category triclinic space group Pl a 7.447 < 2) A b 13.834 (3) A c 15.225 (3) A a 112.93 ( 1). 143730.doc 201026668 Parameter β 98.06(1)0 Ί 97.96(1) ° Volume 1397.9(2) A3 Ζ 4 Density (calculated value) 1.328 e/A3 R1, wR2 0.059, 0.126 a, b, c = boundary length of unit cell α, β , γ = angle of unit cell Ζ - number of molecules in the early crystal cell

The DSC measurement of the herbicide and the crystallized complex of the herbicide showed an endothermic melting peak at 55 to 57 C and the highest peak at 59 to 62 〇c. Thus, the melting point of the crystalline complex is close to the melting point of the known ruthenium-modified material and is 4 to 2 inches lower than the refining point of the herbicide. The crystal complex of the present invention can be obtained by co-crystallizing the herbicide from the solution containing the herbicide and the hydrazine or by allowing the liquid or the melt to be crystallized. Similarly, A can be prepared by combining (or separately mixing) a hydrophobic suspension and an aqueous suspension of the herbicide, and the process is preferably carried out at a heating temperature, for example, above 3 (TC). In a preferred embodiment of the process for the preparation of the crystalline compound of chlorfenapyr and schistosomiasis, the herbicide and the armored product of the mixture of the herbicide and the herbicide or the specific agent of the organic solvent are used. The liquid is filled with the wrong substance. Therefore, the method includes suspending the herbicide and the saponin in an organic solvent or the water and the liquefaction process. a mixture of various agents and compositions (thus referred to as a preferred organic solvent for the liquefaction process or a mixture of water and an organic solvent 143730.doc 201026668 is a solvent having similar solubility to samarium and chlorfenapyr. Solubility means that the solubility of each of the compounds in a solvent or solvent system differs by no more than 20%, preferably by no more than 1%. However, a solvent or solvent system in which the solubility of the compound is not similar may also be used. The compounds having higher solubility in the solvent or solvent system may preferably be used in excess. The preferred organic solvents for the liquefaction process are those which are at least partially miscible with water, that is, at room temperature with water. Preferably, at least 丨〇% v/v is at least 20% V/V, and mixtures thereof. Similarly, it is preferred that the at least partially water-miscible solvent has a water miscibility of less than 1% at room temperature. A mixed solvent of an organic solvent of Wv. Preferably, the organic solvent comprises at least 80% v/v of at least one at least partially water-miscible organic solvent, based on the total amount of the organic solvent. Suitable solvents for 10% water miscibility include, but are not limited to: 1 _ Ci-C4 alcohol, such as: methanol, ethanol, n-propanol and isopropanol; 2. guanamine 'C^-C: 3 carboxy Acid N-mercaptoamine and n,N-dimethyl decylamine, such as: meglumine, dimethyl decylamine (DMF), acetamidine, keto dimethyl acetamide; Five or six members of a total of 7 carbon atoms, such as pyrrolidine, N-mercaptopyrrolidone, N-ethylpyrrolidone, N-isopropylpyrrole, N-hydroxyethylpyrrolidone, Piperidone, N_mercaptopiperidone, caprolactam, or N-decyl caprolactam; 4. Diterpenoid and sulfolane; 143730.doc -10· 201026668 5. 3 to 6 a ketone of a carbon atom such as: acetone, 2-butanone, cyclopentanone and cyclohexanone; 6. acetonitrile or propionitrile; 7. a five or six member lactone such as γ-butyrolactone; And multiple shouts, such as ethylene glycol, glycerin, dimethoxane, diethylene glycol, ethylene glycol monomethyl ether; 9. cyclic carbonates with 3 to 5 carbon atoms, including propylene carbonate and carbonic acid Vinyl ester; and 10. dimethyl (poly)CyC3·stretching glycol ether '如: Dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dioxime ether, dipropylene glycol dimethyl ether, low molecular weight polyethylene glycol and low molecular weight polypropylene glycol (MW £400) ° Preferably, it is a group 1 organic solvent, and a mixture thereof with water. In the mixture with water, the relative content of 'organic solvent and water can vary from 1:2 〇〇 (v/v), specifically It is between 1:5 and 1: ι〇〇(ν/ν). The slurry is prepared by suspending the herbicide and the guanidine in a solvent or a solvent/water mixture. Choose the herbicide, the guanidine and the solvent. Or the relative amount of solvent/water mixture to obtain a suspension at the specified temperature. It should be avoided that the herbicide and the herbicide are completely dissolved. Specifically, the herbicide and the herbicide are suspended in a solvent or solvent/water mixture in an amount of from 1 g to 500 g per liter, preferably from 1 至 to 4 〇〇 g. In the process of polyliquefaction, depending on the relative > degree of solubility of the herbicide and the hydrazine in the selected solvent or solvent system, the relative molars of the herbicide and the samarium 143730.doc 201026668 may be between 1:100. Between 100:1, preferably between 1:1 〇 and 1 〇: 1 ° In a solvent system with similar solubility for both pure herbicide and samarium, the preferred molar ratio is between 2 Between 1 and 1:2, in particular between 1.5:1 and 1:ι·5, and especially about 1:1 (ie, i 1:1 to 1:1 has a higher solubility for sputum) In the solvent system, the applied hydrazine will be used in excess. This is the case for the herbicide, and vice versa. If one of the components exceeds the stoichiometry of the crystalline complex, a mixture of the crystalline complex and the excess compound will be obtained. , but the excess is usually dissolved in the mother liquor (especially if the excess compound is used in the solvent system of choice). For the formulation, acceptable application of hydrazine or chlorfenapyr is acceptable. Excessively, in particular, the presence of an excess of metochlor does not pose a problem of stability. The pure crystalline complex is prepared. The relative molar amount of the herbicide and the guanidine is close to the stoichiometry required to form the complex, and the value generally does not deviate from the desired stoichiometric amount of 5 〇 mole percent. The process is usually carried out at a temperature of at least 5%, preferably at least 10 C, in particular at least 2 〇 ° C, for example between 5 and 8 〇. (: between, preferably between 10 and 55 °) Between C, in particular, it is "between it. The time to form a crystalline complex by the liquefaction process depends on the temperature, the type of solvent, and generally takes 2 hours and often at least 6 hours. In any case , can be completely converted after 1 week, but complete conversion usually does not need to exceed 24 hours. According to the embodiment of the present invention, the co-crystal of mesalamine and samarium is carried out as a seed crystal (four) b is usually Based on the total weight of the herbicide and the applied hydrazine, use (ΜΗ·% by weight, preferably (1)% by weight 143730.doc -12- 201026668 and more preferably 0.3 to 2 weight. / 〇 seed crystal. In another In a preferred embodiment of the invention, the crystalline complex is made The process comprises combining hydrazine and chlorfenapyr in an aqueous liquid. The method of combining hydrazine and chlorfenapyr in an aqueous liquid is, for example, by combining a hydrophobic suspension with an aqueous suspension of imazachlor or by applying a hydrophobic suspension The herbicide solid is added to the liquid, or the cerium solid is added by adding the cerium solid in the aqueous suspension of the herbicide or the hydrazine and the herbicide are suspended in the aqueous liquid. Thus, the aqueous suspension is obtained, which is suspended in the aqueous liquid as a solid material. The form comprises the herbicide and the herbicide. The aqueous suspension obtained in this manner comprises the crystalline complex of the herbicide and the herbicide in the form of suspended particles, and optionally the excess of the applied sputum and/or the herbicide in the form of suspended particles. amine. The combined application of hydrazine and chlorfenapyr in an aqueous liquid is preferably also accompanied by the application of shear forces in an aqueous suspension comprising hydrazine and herbicide obtained in this manner. The application of shear forces generally accelerates the conversion of the herbicide and the applied hydrazine to a crystalline complex. This particularly preferred embodiment is also referred to hereinafter as the "shearing process". Preferably, the hydrazine and the herbicide are applied in an aqueous liquid and/or the shearing force is applied to the aqueous liquid mixture obtained in this manner preferably at least 1 C, often at least 2 C, preferably at At least 3 weeks old. Specifically, it is carried out at 35 ° C (for example, 15 ° C to 80 ° C, preferably "it goes to it, specifically 3 CTC to 55. (: or 35 ° C to 50 ° C). The herbicide is usually present in the liquid medium in the form of solid particles. However, for the herbicide, it is not - defined as a solid during processing - and may be more advantageous if the temperature is near or above its melting point. The application of shearing force to the liquid mixture accelerates the formation of the crystalline complex. 143730.doc -13· 201026668 In the aqueous liquid combining the herbicide and the hydrazine, the main component of the liquid medium is water, which may contain up to 20%. % v / v water-miscible solvent, specifically one of the solvents belonging to Group 1 and / or Group 8 as a main component. In addition, the aqueous liquid may also contain additives usually present in liquid suspension concentrate The content of the herbicide and the hydrazine obtained in the aqueous suspension obtained by combining the herbicide and the hydrazine in the aqueous liquid may be between 5 and 70% by weight based on the total weight of the suspension obtained in this manner, in particular, 1 〇 Up to 6% by weight and more preferably 15 to 50% by weight. The aqueous suspension obtained by combining the herbicide and the hydrazine in an aqueous liquid may comprise a relative molar ratio of between 1:5 and 20:1 (preferably between 1:1.2 and 15:1). Metamine and guanidine. If one of the components exceeds the stoichiometry of the crystalline complex, a mixture of the crystalline complex and the excess compound will be obtained. For the purpose of the formulation, an excess of the herbicide or the lanthanide is present. In particular, the excessive presence of mesalamine does not cause stability problems. However, based on the content of the herbicide in the mixture, the content of the hydrazine in the aqueous suspension is preferably not more than 2 〇 mol% by weight. Specific, in particular, not more than 10% by weight. Therefore, the present invention is specifically directed to a liquid formulation comprising the crystalline complex of the present invention, but with the proviso that if the herbicide and the herbicide are _ or Both of them are present in the formulation in a non-coincident form, and the content of the non-miscible sputum in the formulation is not more than 20 mol%, in particular, no more than 10 mol%. Oxalamine and _ The liquid medium of the aqueous suspension may comprise the addition of I43730.doc 201026668 which is usually present in the liquid suspension concentrate. The following additives are described below and include surfactants, specific = anionic or nonionic emulsifiers, moisturizing The agent and the dispersing agent (usually added to the crop protective composition) further comprise an antifoaming agent, an antifreeze J pH adjusting agent, a stabilizer, an anti-caking agent, a dye and a biocide (preservative). 'The liquid medium does not contain a viscous modifier (thickener). The surfactant content is usually between 0.5 and 20% by weight, based on the total weight of the aqueous suspension, between % and % by weight. And © 4 Temple is better between 1 and 10% by weight. Based on the total weight of the liquid medium and the herbicide and the applied hydrazine, the content of the east agent is up to 1% by weight, specifically 20% by weight (for example, 〇5 to 2% by weight, in particular) As for weight %). The content of the additive other than the antifreeze J and the surfactant may be 5% by weight based on the total weight of the liquid medium and the herbicide and the herbicide. The time required to form the crystalline complex is in a manner known per se, depending on the shear and temperature applied, and can be determined in standard experiments by one of ordinary skill in the art. It has been found that a time in the range of from 1 minute to 48 hours is suitable for the formation of a crystalline complex in an aqueous suspension comprising Φ herbicidal amine and cerium, but it may also be longer. A shear time of from 5 to 24 hours is preferred. In a preferred embodiment, a shear force is applied in the aqueous suspension of the herbicide and the acetonide, which is prepared by combining the hydrazine and the herbicide in an aqueous liquid. A suitable shearing force can be applied by suitable techniques to provide intimate contact between the herbicide and the granules of the herbicide and/or to pulverize the crystalline complex particles. 8 Suitable techniques include grinding, milling or milling ( Especially by wet grinding or wet milling 'including, for example, bead milling or by using colloidal milling powder.) Suitable shearing equipment, including ball mills or bead mills, specifically 143730.doc -15- 201026668 Ball mill, circulating mill (mixing ball mill with pin grinding system), disc mill, ring cylinder mill, double cone mill, three roll mill, batch mill, colloid Mills, and media mills (such as sanders). In order to dissipate the heat generated by the grinding process, the grinding cylinder is preferably equipped with a cooling system. A particularly suitable grinder is the Drais Superflow DCP SF 12 ball mill from DRAISWERKE INC. (40 Whitney Road· Mahwah, NJ 07430 USA), Drais Perl Mill bead mill (PMC) from DRAISWERKE INC., available from Netzsch- Feinmahltechnik GmbH's ZETA cycle grinding system, available from Netzsch Feinmahltechnik ❹ GmbH (Selb, Germany) disc mill, Eiger Mini 50 bead mill from Eiger Machinery Inc_ (888 East Belvidere Rd., Grayslake, IL 60030 USA) And the DYNO-Mill KDL bead mill from WA Bachofen AG (Switzerland). However, other homogenizers are also suitable, including high shear mixers, Ultra-Turrax units, static mixers, such as systems with mixing nozzles, and other homogenizers (such as colloid mills). In a preferred embodiment of the invention, the shearing is performed by a bead mill. special

In the case of Q, it is found that the bead size is between 0.05 and 5 mm, more specifically between 0.2 and 2.5 mm and most particularly between 0.5 and 1.5 mm. A bead load of between 40 and 99%, in particular between 70 and 97%, and more particularly between 65 and 95% is typically used. After a sufficient shearing force is applied, a suspension of the crystalline complex is obtained, optionally mixed with an excess of the herbicide and/or the cerium, wherein the particle size of 90% by weight of the suspended particles is not greater than that determined by dynamic light scattering. 30 μηη, preferably not more than 20 μηη, specifically no more than 10 μηι and especially no more than 5 143730.doc •16· 201026668 μηι. The liquid suspension of the crystalline complex obtained in this manner is converted by conventional drying methods (specifically by spray drying or freeze drying) after the addition of the additive to the formulation or, in particular, prior to the addition of the additive. Into the powder group σ. Drying or spray aids can be added before or during drying. Suitable drying or spray auxiliaries for drying aqueous dispersions are known. These include protective colloids such as: polyvinyl alcohol, specifically hydrolysis degree ❹ > 7〇% of polyethylene glycol), carboxypolyvinyl alcohol, benzenesulfonic acid/formaldehyde concentrate, benzenesulfonic acid/urea/formaldehyde Condensate, naphthalenesulfonic acid/formaldehyde condensate, naphthalenesulfonic acid/formaldehyde/urea condensate, polyvinylpyrrolidone, maleic acid (or maleic anhydride) and vinyl aromatics (such as styrene and its ethoxylation) a copolymer of a derivative, a copolymer of maleic acid or maleic acid and a C2-C1 () dilute hydrocarbon (such as diisobutylene and an ethoxylated derivative thereof), a cationic polymer (for example, an N-alkane) a copolymer of a base_N_vinylimidazolinium compound and a N-vinyl decylamine, and an inorganic anti-blocking agent (sometimes referred to as an anti-caking agent), such as: Shi Xi Acid, φ Specially called coking vermiculite, alumina, calcium carbonate, etc. The amount of the drying aid is usually from 0.1 to 20% by weight based on the weight of the active compound particles in the liquid pesticide composition of the present invention. As already mentioned above, the crystalline complexes as defined herein are suitable for the preparation of crop protection compositions, in particular for the preparation of aqueous suspension concentrates. Accordingly, the present invention also provides an agricultural composition for crop protection comprising a crystalline complex as defined herein, (if appropriate) a liquid carrier liquid phase or a solid carrier and/or one or more conventional Auxiliary agent. Applicable liquid/liquid carrier water, which contains trace water miscible as needed 143730.doc •17· 201026668 organic solvent' (eg solvent of groups 1 to 10) and low solubility for sedative and chlorfenapyr Or organic solvent insoluble or not, 'for example, at 25. At 〇 and 1 〇 13 mbar, the solubility of sevodoxime and imazachlor in the solvents is not more than 1% by weight 'specifically not higher than 0.1 weight (four) and especially not higher than 0.01% by weight. Suitable solid carriers are in principle all solid material baskets which are used in crop protection combinations (specifically in fungicides) when used as a τ*. Solid carrier system example 'mineral soil (such as: Shixijiao, Shixi acid salt, stagnation clay, white cloud synthetic material grinding soil, limestone, lime, chalk, red basalt soil, loess, stone, diatomaceous earth, sulfuric acid Calcium and magnesium sulfate, magnesium oxide), powder, fertilizer (such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea) and plant source products (such as: powder, bark powder, wood powder and nut shell powder, Cellulose powder) and other solid carriers. Typical adjuvants include surfactants (especially humectants and dispersants commonly used in crop protection compositions), further comprising viscous modifiers (thickeners), defoamers, antifreeze, pH adjustment Agents, stabilizers, anti-caking agents and biocides (preservatives). In particular, the invention relates to crop protection compositions in the form of a suspension concentrate, in particular an aqueous suspension concentrate (SC). The suspension concentrate comprises a crystalline complex in the form of fine particles and a liquid carrier (=liquid medium/liquid phase), in particular an aqueous carrier (=aqueous medium/aqueous phase), wherein the crystalline complex particles are Suspended in a liquid carrier, preferably an aqueous carrier. The particle size of the active compound (i.e., no more than 90% by weight of the active compound) is typically no greater than 3 μm, preferably no greater than 2〇143730.doc • 18· 201026668, as determined by dynamic light scattering. Μιη, specifically no more than 10 μηι, especially no more than 5 μιη. Preferably, at least 40% by weight and in particular at least 6% by weight of the particles in the SC according to the invention have a diameter of less than 2 μηι. Suspension concentrates, in particular aqueous suspension concentrates, may be prepared by suspending the crystalline complex in a suitable aqueous carrier which may contain the customary formulation additives described below (if appropriate, the suspension actives may then be ground (1) Columns, grinding or milling)). Preferably, however, the suspension concentrate should be prepared via the shearing process described herein, i.e., by applying a shear force to the liquid comprising the herbicide and the sputum suspension particles and optionally including other active agents. In addition to the crystalline complex, the suspension concentrate typically comprises a surfactant, and, if appropriate, an antifoaming agent, a thickening agent, an antifreeze, a stabilizer (biocide), a devaluation modifier, an anti-caking agent. And other possible active compounds. In such SCs, the amount of active compound (i.e., the total content of the crystalline complex and, if appropriate, other active compounds) is usually from 10 to 70% by weight, based on the total weight of the suspension concentrate, specific 15 to 5 % by weight. Preferred surfactants are anionic and nonionic active agents (emulsifiers). Suitable surfactants can also be protective colloids. The surfactant content is usually from 〇5 to 2% by weight, particularly from 1 to 15% by weight and particularly preferably from 丨 to (7)% by weight, based on the total weight of sc according to the invention. Preferably, the surfactant comprises at least one anionic surfactant and at least one nonionic surfactant, the ratio of the anion to the nonionic active agent being typically between 10:1 and 1:10. Examples of anionic surfactants (anionic surfactants, emulsifiers, and dispersions 143730.doc -19-201026668) include alkyl aryl sulfonates, phenyl sulfonates, alkyl sulfates, decanoates , alkyl ether sulfate, alkyl aryl sulphuric acid vinegar, dad polyglycol ether phosphate, polyaryl ether phenyl phosphate, alkyl sulfonate, alkyl sulfonate, paraffin Sulfonate, petroleum based acid vinegar, tauride, sarcoside, fatty acid, alkyl naphthalenesulfonic acid, naphthalenesulfonic acid 'lignin sulfonic acid, sulfonated naphthalene and formaldehyde or Condensate with methacrylate and benzene and, if appropriate, urea, and benzoic acid, condensate of methylate and urea, lignin sulfite waste liquor and lignosulfonate, alkyl phosphate, alkyl An aryl phosphate (for example, a tris-styrene phosphate), and an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and an amine salt of the above substances. The preferred anionic surfactant is an anionic surfactant having at least one acid-reducing group and, in particular, an alkali metal salt thereof and an ammonium salt thereof. Examples of nonionic surfactants (nonionic emulsifiers and dispersants) include alkylphenol alkoxides, ethanol alkoxides, fatty amine alkoxides, polyoxyethylene glycerin fatty acid esters, castor oil alkoxides, fatty acids Aloxoxide, fatty decyl alkoxide, fatty polyglycolide, lanolin ethoxylate, fatty acid polyglycol ester, isotridecyl alcohol, fatty decylamine, fluorenyl fiber Q, fatty acid ester, Alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol base, polyethylene glycol / poly Propylene glycol mystery segment copolymer (polyepoxyethylene/polyoxypropylene block copolymer) and mixtures thereof. Preferred nonionic surface m agents are fatty alcohol ethoxylates, alkylated polysaccharides, glycerol fatty acid S, ramie smear and ", burned oxides, fatty acid oxides, fatty amine burned oxides, wool > Surface-rolled, fatty acid polyglycol esters and epoxy 143730.doc -20- 201026668 Ethylene/propylene oxide block copolymers and mixtures thereof. Protective colloids are typically water-soluble amphoteric polymers. Including proteins and denatured proteins, such as: casein, polysaccharides (such as: water-soluble starch derivatives and cellulose derivatives, specifically hydrophobically modified starch and cellulose) 'in addition to polycarboxylates (eg polyacrylic acid) (Polyacrylate), acrylic or methacrylic copolymer or maleic acid copolymer (eg acrylic/olefin copolymer, acrylic/styrene copolymer, maleic anhydride/olefin copolymer (eg Sokalan® CP9, BASF) SE)) and esterification of the copolymer with polyethylene glycol, polyketene, polyvinylpyrrolidone, vinylpyrrolidone copolymer, polyvinylamine, polyethyleneimine and poly(alkylene ether) Product. In principle, the SC according to the present invention comprises at least one surfactant (wetting agent) capable of improving the wettability of the plant part in an aqueous application form and at least one surfactant capable of stabilizing the dispersion of the active compound particles in the SC (stable The content of the humectant is typically between 0.5 and 10% by weight, in particular between 0.5 and 5 weights ◦/◦, and especially between 〇·5 and 3, based on the total weight of the SC. Between the weight %, the dispersant content is typically between 0.5 and 1% by weight and, in particular, between 5 and 5% by weight, based on the total weight of sc. Preferred wetting agents are anionic or Nonionic, and selected from, for example, naphthalenesulfonic acid (including alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts), in addition to fatty alcohol ethoxylates, polyglycosides, glycerol fatty acid esters, castor oil Alkoxide, fatty acid alkoxide, fatty decyl alkoxide, fatty polyethanolamine, lanolin alkoxide, and fatty acid polyglycol ester. Preferred dispersants are anionic or nonionic and are selected, for example, from Poly(ethylene)/polypropylene glycol block copolymerization , polyethylene glycol alkyl ether, polypropylene glycol I43730.doc -21- 201026668 alkyl ether, polyethylene glycol / polypropylene glycol ether block copolymer, alkyl aryl phosphate s (such as stilbene phosphate) , lignin sulfonic acid, sulfonated naphthalene and formaldehyde or condensate with formaldehyde and phenol and (if appropriate) urea, and condensate of benzenesulfonic acid, furfural and urea, lignin sulfurous acid waste liquid and lignosulfonic acid Esters, polycarboxylic acids such as 'polyacrylates, maleic anhydride/olefin-based copolymers (eg Sokalan® CP9, B ASF SE), including the alkali metal salts, soil test metal salts, money salts and amines of the above substances A viscous/modifying additive (thickener) suitable for use in the SC according to the present invention is a compound which imparts a pseudoplastic flow property to a formulation, that is, a high viscosity in a standing state, but is stirred. In the state, it has low viscosity. Suitable thickeners are in principle all compounds which are used for this purpose in suspension concentrates. It may, for example, be an inorganic substance such as bentonite or attapulgite (such as Attaclay® (available from Engelhardt)), and organic substances such as polysaccharides and heteropolysaccharides (such as Xanthan Gum® (Kelco® (purchased from Kelco)), Rhodopol® 23 (Rhone P〇ulenc) or Veegum® (purchased from RT vanderbiit) and preferably Xanthan-Gum®. Usually, the viscosity-modifying additive is present in an amount of from 1 to 5% by weight based on the total weight of 8 (:. The antifoaming agent suitable for the SC according to the invention is, for example, known for this purpose. Polyoxylized emulsion (Silikon® SRE (available from Wacker), or Rhodorsil® (available from Rhodia)) 'Long-chain alcohols, fatty acids, aqueous terpene dispersion-type defoamers, solid antifoams (so-called compounds) The organic fluorine compound and the mixture thereof. The content of the antifoaming agent is typically between 11 and 1% by weight based on the total weight of the SC. A preservative may be added to stabilize the suspension concentrate according to the present invention. 143730.doc •22- 201026668 Preservatives are their isothiazolone-based preservatives, for example, Proxel<S> (from ICI) or Acticide® RS (from Thor Chemie) or Kathon® MK (purchased from R 〇hm & Haas). The bactericide content is typically between 0.05 and 0.5% by weight based on the total weight of SC. Suitable antifreezes are liquid polyols such as ethylene glycol, propylene glycol or glycerol. The total weight of the suspension concentrate, the content of the antifreeze is usually between 1 and 20% by weight, Specifically, it is between 5 and 1% by weight. If appropriate, an example in which the SC according to the present invention may contain a buffer pH buffer for adjusting the pH is an alkali metal salt of an inorganic weak acid or an organic weak acid, for example, For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid, and succinic acid. If the seed is treated with a formulation of a crystalline complex, it may contain other conventionally used seeds (eg, mixing In addition to the above ingredients, examples thereof are specifically defined as colorants, adhesives, fillers, and plasticizers. Conventional colorants used for this purpose are dyes or pigments. In this context, Water-soluble dyes and water-soluble dyes are used. Examples which may be mentioned are dyes and pigments known by the following names: Rhodamine B, c. j• Red pigment 112 and CI Red Solvent 1, Blue pigment 15:4, blue pigment 15:3, blue pigment 15:2, blue pigment 15:1, blue pigment 80, yellow pigment!, yellow, red pigment 48:2, red pigment 48:1, red pigment 57:1 , red pigment"], orange pigment 43, orange pigment 34, orange pigment 5, green 36, green pigment 7, white pigment 6, standard pigment 25, test purple 10, test purple 49, acid red 51, acid red 52, acid red U, acid blue 9, acid yellow 23, test red 〇, Authentic red 143730.doc -23· 201026668 108. In terms of the total weight of the formulation, the color of the coloring agent; sa 逋 逋 * not more than 20% by weight and preferably between 〇 · 1 to 15 weight Between %. Adhesives can be used as a conventional bonding sword for seed dressing products. Examples of suitable binders for humans and ώm include thermoplastic polymers (such as polyvinylpyrene B, -, polyvinyl acetate vinegar, (10) alcohol and cellulose acetate, others are polyacrylic acid, polymethyl Alkyl acrylate, polybutene, polyisobutylene, poly cage + c*, polyethylene diamine, polyvinyl decylamine, protective colloids, polyester, polyether ester, monoacid, polyacetamide Carbamate vinegar, polyacetamide 'thermoplastic..., such as polycellulose derivatives' such as: fiber (four), cellulose bond, cellulose bond, including thiol cellulose, ethyl cellulose, m methyl fiber , methyl cellulose, hydroxypropyl cellulose and starch derivatives, and modified starch, paste: ', maltodextrin, brown acid and chitosan, in addition to fat, oil, protein ( Including casein, gelatin and zein), gum arabic, worm knees. Preferred adhesives are biocompatible, ie those that are not significantly phytotoxic. Preferably, the adhesive is biodegradable. Preferably, the adhesive of choice is used as a substrate for the active ingredient of the formulation.总 The total weight of the formulation, the amount of the adhesive is not more than the weight of the peach and preferably between 丨 to 姆%, and in particular between $ to (four) 5%. The external 'mixture may also contain an inert filler. Examples thereof include the above solid carrier materials', especially clay, self-desired, bentonite kaolin, talc, perlite, mica, Shi Xishi, Shiyoshi, quartz powder, The fine-grained inorganic material of montmorillonite, which may also be a fine-grained organic material such as wood powder, sputum powder, activated carbon, etc., and the total weight of all non-volatile components in the formulation is 143730.doc -24- 201026668 Preferably, the filler content is selected to be no more than 75% by weight in total. Typically, the filler is present in an amount ranging from 1 to 50% by weight, based on the total weight of all non-volatile components in the formulation. The formulation may also contain a plasticizer which increases the flexibility of the coating. Examples of plasticizers include polyolefin diols, glycerin, dialkyl phthalates, alkylphenyl phenyl phthalates. Phthalate esters, ethylene glycol benzoates and related compounds. The plasticizer content of the coating is often between 0.1 and 20% by weight based on the total weight of the material. The crystalline complex of the present invention can be used in a manner known per se for combating/controlling undesirable vegetation. In particular, the crystalline complex can be formulated with other active compounds to increase activity and/or broaden the range of activity. Therefore, it is preferably applied in combination with other herbicides or in a mixture with other crop protection agents (eg, It may be advantageous with the agent used to control pests or phytopathogenic fungi or bacteria. It should be noted that it is miscible with mineral salt solution (for the treatment of nutrients and trace element deficiency). Other additives may also be added. If non-phytotoxic oils and oil concentrates are used in combination, the crystalline complex of the present invention should preferably be applied with herbicides and other pesticides (usually used in the application). Thus, the preferred embodiment of the invention relates to an agricultural composition comprising at least one other active compound in addition to the crystalline miscible sigma. Preferably, the agricultural composition is in the form of a suspension concentrate comprising, in addition to the crystallized material of the present invention, fine particles of at least one other active compound. In principle, the formulation of the #crystal complex according to the invention can be used against 143730.doc • 25- 201026668 undesired vegetation and all plant diseases caused by harmful fungi and other pests, which can be used as a conventional formulation of the applied sputum and It is countered by a combination of other pesticides. The formulations of the present invention are generally suitable for controlling a wide variety of harmful plants, including monocotyledonous weeds, in particular one of the annual weeds, such as grass weeds (grass), including genus, such as eucalyptus (Echinochloa crusgalli var. Crus-gcz//z·); genus, such as horsegrass saAZgwiwa/h); foxtail, such as Setaria viridis, Setaria faberii, sorghum, such as sylvestris Perennial, such as wild oats (Jvewa; forbidden genus, such as Cenchrus echinatus; brome; ryegrass; valerian; wild genus; genus; genus; Annual bluegrass (10); Alopecurus myosuroides · Aegilops cylindrica 'jgropyron (pera venti), Eleusine indica, dog Cytodon dactylon~. This formulation is also suitable for many species of dicotyledonous weeds, especially broad-leaved weeds, including the genus P〇丨ygonum convolvolus, 1 phoenix, Amaranthus retroflexus » 黎属' as red heart 藜 · (Ch Enopodium album L.); yellow in inspection, such as thorn lake (S/afii ίρίπσία L.); genus genus, such as the American sage; thorn genus; chamomile; atrin; genus; Genus; genus of genus; genus of genus; genus of genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, genus 26- 201026668 Genus; Matricaria; Garlic Mustard; Solanum Solanum; Xanthium; Pompadata; Amaranthus, Stellaria media, 'Abuti.lon theophrasti, Dasutian Bin (sesbania exaltata Cory)., there is a distance from the flower sunflower and crbi price α); Bidens (price heart corpse; field mustard {Brassica kaber), meal (jJapsella bursa-pastoris) ·, Chrysanthemum (CewiaMreo ; wild sesame (Ga/eophs; pig 殃

(Ga/hm a/?aW«e); to the hollyhock α (10) mws); South American arboreal [Desmodium tortuosum], it 滨 (Kochia scoparia), 散散花(Mercwrz'aD α(四)wfl); (M less osoib flrvewh·?); Papaver rhoeas ·, Raphanus raphanistrum., thorn sand (>Sa/j〇/<3 moxibustion α/ί); wild fen; Treasure (SowcAms arveai/·?); blue cabbage (TTz/a^z·arvewe); Tagetes minuta, Richardia brasiliertsis and so on. The formulation is also suitable for controlling many kinds of annual evergreen sedge weeds, including sedge weeds such as fragrant aconite (Cjyperw·? Z.), yellow sedge (Cyperus esculentus L.), and mulberry (Cyperus) Brevifolius Η.), sedge (Cyperw·? wicrozWa • Siewd), broken sedge (Cxperws i) ia L. The formulation of the present invention is particularly suitable for controlling monocotyledonous and dicotyledonous weeds and sedges, in particular, A. maiden, A. cerana, wild oats, genus, genus, genus, genus Genus, genus, genus, genus, genus, genus, genus, genus, genus, genus, bluegrass, genus, genus, genus, genus, genus, chamomile, Atriplex, Tianfen, Amaranth, Amaranthus, Liquorum, Euphorbia, Poria, Kochia, Bao 143730.doc -27- 201026668 Capreolum, Matricaria, Aphis, Aphis, Wild radish, wild mustard, sorghum, Solanaceae, garlic mustard, blue cabbage, genus, genus, genus, genus and sedge. Formulations in accordance with the present invention are particularly useful for combating/controlling harmful plants in beneficial plants (i.e., crops). These blending*s are generally suitable for combating/controlling undesirable vegetation in the following plants: - grain crops, including for example: - cereals such as wheat aeWz'vww) and wheat crops such as durum wheat (Γ. durum) ), T. monococcum, Emmer (77. and Spelt (Γ. Seca/e cerea/e), Black Wheat (ZWiioieca/e), Barley (Hordeum vulgare) ·, _ maize (maize; corn; Zea mays) - sorghum (eg sorghum 6/co/owr)); - rice (rice, such as rice (Oryza · 5 < 3 ί · Ζ · νί2) and light glutinous rice (Oryza Glaberrima)) ', anti-cane curtains; - legumes (Fafeaceae) including, for example: soy), peanuts (paraffin (jrac/n··? and pod crops (eg cowpea, including cowpea (P/JW/) W ia/Z'VWTW), Beans, and Red Beans, including Beans, Rhododendron (F-type "α" and "Phaseolus spp", "Anti-4, Jens culinaris var.") - Cruciferae Including, for example, Canadian canola (jBrim/co! napws), Brassica napus (Brawica, cabbage (_β· o/erac*ea 143730.doc -28 - 201026668 v Ar.), mustard (such as mustard-type rapeseed (10,000, cabbage type rapeseed (10,000

Campestris), radish (β· narin_), black mustard (β ( (4), β (a male sterile line of mustard-type rapeseed) and broccoli (Brassica rapa var.)) - other broad-leaved crops including Hollyhock, cotton, flax, linen, beet, potato and tomato; _ booty (TNV: tree) plus (nut) and ▲ (vine) include

For example, grapes, citrus, pome fruit (such as fruit, pear, coffee, pistachio and oil palm), stone fruit (such as peach, almond, walnut, eucalyptus, floor peach, plum, apricot); _ grassland, pasture and pasture; - Onions and garlic; - Ball-shaped ornamental plants such as tulips and narcissus; Trees and deciduous trees such as Pinus massoniana, Chinese fir, oak, maple, sylvestris, Hawthorne, sea bream, and buckthorn (sea buckthorn); Plants such as petunia, marigold, rose and snapdragon. The composition of the present invention is particularly suitable for combating undesirable vegetation in the following crops: barley, rye, triticale, durum wheat, rice, jade; a cane, a large, pod bean crop (such as peas, Soybeans and lentils, peanuts, 6 η 1 * ° ^ vegetables, horse yam, cotton, cruciferous crops (such as European rapeseed, Canadian and steamed clams), lawn, grape cabbage, stone fruit (such as peach , almonds, walnuts, eucalyptus, plums, apricots, citrus and pistachios. The composition according to the present invention can also be used for genetic engineering and breeding to resist 143730.doc •29· 201026668 crops resistant to one or several herbicides, capable of resisting one or several pathogenic bacteria (such as fungi due to genetic engineering and breeding) Crops, or crops that are resistant to insect attacks due to genetic engineering and breeding. Suitable crop examples are, for example, preferably resistant to crops such as applied corn, wheat, sunflower, rice, canola, Brassica napus, soybean or lentils, or resistant to specifics due to the introduction of the tau toxin gene via genetic modification. Insect attack crops. The compositions of the present invention can be applied in a conventional manner using techniques familiar to those skilled in the art. Suitable techniques include spraying, atomizing, spreading or watering. The mode of administration is in a conventional manner and, for the purpose of administration, the optimum uniform distribution of the active ingredients in accordance with the present invention should be ensured in any case. The composition can be applied prior to or after germination, for example, prior to, during, or after germination of undesirable vegetation. When the composition is used in crops, it can be applied after sowing and before or after germination of the crop. However, the composition of the present invention can also be applied before the crop is planted. The composition is applied primarily to the vegetation by spraying, in particular the soil spray method and the leaf spray method. It can be carried out by conventional spray techniques, for example using water as a carrier, and spray liquids between about 10 and 2000 liters/ha or between 5 and 1000 liters/ha (for example between 100 and 500 liters/ha). Proportion of application. The compositions can also be administered in low and ultra low doses. If some crops are less tolerant to the active ingredient, the application of the spray spray composition can be used to minimize the contact of the composition with the leaves of the sensitive crop (if contacted) while at the same time reaching the growth site I43730.doc • 30- 201026668 Blades of undesirable vegetation in the lower or bare soil (p〇st. directed, iay_by). If the plant is treated after germination, the herbicide mixture or composition according to the invention is preferably applied via the leaves. For example, a conventional spray technique is employed in which water is used as a carrier and the mixture is sprayed at a dose of about 5 Torr to 1 liter per hectare. The desired application ratio of the composition of the pure active compound (i.e., the herbicide, the herbicide and optionally other active compounds) is based on the unequal planting density, the plant growth stage, and the climatic conditions at which the composition is applied. And the method of application is determined. In general, the active substance application rate of the composition (the total amount of sputum, herbicide and other compounds optionally used) is between 15 and 5 00 g/ha, preferably between 2 and 25 gram. /ha. The complex of the present invention can be formulated in a manner known per se with other compounds which exhibit activity against undesirable vegetation, phytopathogenic fungi and other pests. In this regard, it has proven to be particularly advantageous to co-distribute crystalline skeptics with at least one other activity that is also active against undesirable vegetation. Accordingly, one embodiment of the present invention is directed to a formulation comprising the crystalline complex of the herbicide and the herbicide of the present invention in combination with one or more imidazoline herbicides. The imidazolinone herbicide is free from shaner, D. L. nner, S. L. "The p; salimone herbicide (The j; midaz〇iinone

Herbicides)" (CRC Press Inc, B〇ca Rat〇n,

Florida 1991) and the Compendium of Pesticide mon Names http://www.alanwood.net/pesticides/) are known. Preferred imidazolinone herbicides include oxime imazeth 143730.doc -31 · 201026668 (imazamox), methoxy acid (imazapic), imazapyr, imazaquin, P. imazethapyr, its salt and its vinegar, and mixtures thereof. In this embodiment, the relative weight ratio of the applied hydrazine and the oxazolinone herbicide is preferably between 1:200 and 200:1, specifically between 1:50 and 50:1, and more preferably 1:10 to 10:1. The novel crystalline complex can be prepared as a low-solvent or solvent-free aqueous suspension concentrate which can be prepared separately or prepared with other crop protection agents, in particular the above-mentioned mixed objects. The solvent content, in particular the content of the aromatic hydrocarbon after deducting the anti-east agent, usually does not exceed 2% by weight of the suspension concentrate, often less than 2% by weight. The characteristics of the suspension concentrate according to the present invention are particularly advantageous in that it has better storage stability than a suspension concentrate or suspension emulsion concentrate which is known to contain a mixture of sputum or samarium and chlorfenapyr. Analytical method: X-ray powder diffraction pattern (PXRD) was taken using a D-5000 diffractometer (purchased from Siemens) with a copper anode (λ = 1.5406 A; 45 kV, 25 mA) with a reflection geometry of 2θ = 4°-35° in increments of 0.02° (at 25°C). The measured value of 2 Θ is used to calculate the interplanar spacing d shown. Single crystal X-ray diffraction. Data at 103(2)K was collected on a Bruker r AXS CCD detector using graphite-monochrome CuKa rays (λ = 1.54178 A). The Fourier techniques with the SHELX-97 suite of software were used to resolve, actuate and amplify the nodules using a direct method. Thermal Gravity/Differential Thermodynamic Analysis (TG/DTA) was performed using Mettler Toledo TGA/SDTA 851 and using Al2〇3 as reference 143730.doc -32- 201026668. The sample (8-22 mg) was placed in a platinum sample cup for testing. Use 30 to 605. (:, 1 〇 ° C / min temperature program and nitrogen flow. Differential scanning calorimetry (DSC) was performed on a Mettler Toledo DSC 823e with a TS0801RO Sample Robot autosampler and TS08006C1 gas control. At 5 ° C / The test was carried out using a heating rate of min and an aluminum crucible with pinholes at 30 to 1 85 ° C. Preparation Example ® I The liquefaction process was carried out with 498 mg of hydrazine and 493 mg of chlorfenapyr (1:1 molar ratio). Add to a mixture of 20 ml of water and ethanol (19:1 v/v). 4 Torr. After stirring for 30 minutes under the arm, add about 5 to 1 mg of the herbicide and the eutectic co-crystal. The mixture was stirred for 5 days, then cooled to 23 C, filtered and dried on a clay plate and left to dry at 23 ° C for 16 hours. The results of pxrd showed that the obtained crystal material was a co-crystal of mesin and a sputum (characteristic pxRD pattern). Shown in Figure 1). The crystalline complex is at 57. The enthalpy begins to melt. The 调 shearing process uses the following formulation additives: 5 kg samples are prepared according to the formulation shown in the table below (all doses are indicated). Except for xanthan gum and green pigment dispersion) Mix in the vessel and then use a 600-ml bead mill with a tip speed of 6.7 m/s to deliver the milled powder (8 kg/h) continuously while maintaining the mixture at 2 °c>c. 2 / 育 育 胶 solution and dye formulation to the resulting mixture to obtain a uniform low viscosity green opaque liquid. The dispersion phase was measured in a 100-fold diluted aqueous solution by laser diffraction 143730.doc -33 - 201026668 The particle size showed that the particle size of 90% of the particles was less than 3.9 μηη (D9〇 value). The sample was evaporated to dryness. The PXRD results of the obtained material showed that in addition to the excess of the herbicide, the crystals of the herbicide and the herbicide were present. Complex compound. Shide 圃42 herbicide 378 glycerin 70 dispersant 1 30 dispersant 2 19 dispersant 3 6 defoamer 5 xanthan gum (2% aqueous solution) 55 dye formulation 1 〇〇水295

Dispersant 1: Ring I B-sinter / oxidized propylene oxime (Pluronic PE 10500; purchased from BASF SE). Dispersant 2 : Acrylic Graft Copolymer (Atlox 4913; purchased from

Unicjuema) ° Dispersant 3: ethoxylated tristyryl ammonium sulfate with 16 ethylene oxide units: Soprophor 4D384; available from Rhodia. Dispersant 4: A salt of a condensation product of benzenesulfonic acid and formaldehyde. Defoamer: Commercially available polyoxyxide defoamer (aqueous emulsion, 20% by weight of activity - Silfoam SRE; available from Wacker Chemie 143730.doc -34-201026668 AG). Dye Formulation: Green Pigment Dispersion Storage Stability: Stability of the ruthenium/paracetachlor co-crystals produced according to the previous examples A 1 g sample was stirred in 20 ml of water at room temperature for two weeks. Then, it was confirmed by a high temperature stage microscope and PXRD that no other crystal form change occurred. BRIEF DESCRIPTION OF THE DRAWINGS The following illustrations and the above examples are illustrative of the invention and are not intended to be limiting

Figure 1 : X-ray powder diffraction pattern of the herbicide and the co-crystal of the herbicide. Figure 2: Asymmetric units (labeled non-carbon and non-hydrogen atoms) of the crystal structure of the co-crystals of mesalamine (left) and enthalpy (right) according to single crystal X-ray analysis. Fig. 3 is a DSC trace diagram of the co-crystal of mesalamine and samarium, which shows an endothermic melting peak at 57 ° C, reaching a peak at about 62 ° C; the heating rate is 10 ° C / min. Figure 4: TGA thermogram of the co-crystals of mesalamine and samarium. 143730.doc 35-

Claims (1)

201026668 VII. Patent Application Range: 1. A crystalline complex comprising pendimethalin and metazachlor. 2. The crystalline complex of claim 1 wherein the ratio of the herbicide to the herbicide is between 0.8:1 and 1.25:1. 3. The crystalline complex of claim 1 wherein 25 is. (: and the X-ray powder diffraction pattern under copper radiation shows at least four of the following reflection values expressed as 2Θ: 6.40±0.2〇λ 7.06±0.2〇' 7.36±〇.2° > 11.82±0.2〇 ' 12.78±〇.2°, 14.72±〇·2〇, 19.21 soil 0.2, 21·28±0.2ο, 22·15±0·2ο. 4_ A crystal mismatch prepared according to any of the above claims And a method comprising the step of suspending the hydrazine and the herbicide in an organic solvent or a mixture of water and an organic solvent. 5. 6. ❹ 7. 8. 9. A preparation as claimed in any one of claims 3 to 3. A method of crystallizing a complex comprising the step of applying a hydrazine and a herbicide in an aqueous liquid. The method of claim 5, wherein the shearing force is applied to the aqueous & float containing the applied hydrazine and the herbicide The suspension is obtained by mixing hydrazine and chlorfenapyr in an aqueous liquid. The agricultural composition 'containing the crystalline complex of hydrazine and imazachlor as claimed in any one of claims 1 to 3. An agricultural composition comprising a crystalline complex of guanidine and imazachlor in the form of an aqueous suspension. The agricultural composition of claim 8 which comprises an additional active compound. 10. The Japanese, 's' of claim 9 wherein the additional active compound is an imidazolinone herbicide. 143730.doc